Substituent effects on chloro meso-tetra-ortho-alkylphenylporphinato iron catalyzed biomimetic oxida

来源 :Chinese Journal of Chemistry | 被引量 : 0次 | 上传用户:gb1107
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Six sterically hindered chloro meso-tetra-ortho-alkylphenylporphinato irons (T(o-R)PPFe(HI)Cl, R = Me, Et, n-Pr, i-Pr, n-Bu, t-Bu) were synthesized and used to catalyze the monooxygenation of cyclohexane with PhIO. Both the yields of cyclohexanol and the relative rates of monooxygenation of cyclohexane catalyzed by T(o-R)PPFe(III)Cl were higher than those of TPPFe(III)Cl respectively. The order of the yields(%) of cyclohexanol and the rate of cyclohexanol formation in the monooxygenation of cyclohexane catalyzed by T(o-R)PPFe(III)Cl for the different substituents are: i-Pr(58) > Et(57) > n-Pr(52) > Me(51) > n-Bu(48) > t-Bu(46) > H(35) and i-Pr > Et > t-Bu > n-Pr > Me > n-Bu > H respectively. The special steric effect on the catalytic character of these different alkyl substituents in T(o-R )PPFe(III)Cl is proposed on the basis of the results. Six sterically hindered chloro meso-tetra-ortho-alkylphenylporphinato irons (T (oR) PPFe (HI) Cl, R = Me, Et, n-Pr, i-Pr, n-Bu, t-Bu) were synthesized and used to catalyze the monooxygenation of cyclohexane with PhIO. Both the yields of cyclohexanol and the relative rates of monooxygenation of cyclohexane catalyzed by T (oR) PPFe (III) Cl were higher than those of TPPFe (III) Cl respectively. The order of the yield ( %) of cyclohexanol and the rate of cyclohexanol formation in the monooxygenation of cyclohexane catalyzed by T (oR) PPFe (III) Cl for the different positions are: i-Pr (58)> Et (57) > Me (51)> n-Bu (48)> t-Bu (46)> H (35) and i-Pr> Et> t- Bu> n-Pr> Me> n-Bu> H respectively. The special steric effect on the catalytic character of these different alkyl substituents in T (oR) PPFe (III) Cl is proposed on the basis of the results.
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